Abstract
Organic semiconductors have received substantial attention as active components in optoelectronic devices because of their processability and customizable properties. Tailoring the organic active layer in these devices to exhibit the desired optoelectronic properties requires understanding the complex and often subtle structure-property relationships governing their photophysical response to light. Both structural organization and molecular orbitals play pivotal roles, and their interactions with each other are difficult to anticipate based upon the structure of the components alone, especially in systems comprised of multiple components. In pursuit of design rules, there is a need to explore multicomponent systems combinatorially to access larger data sets, and supramolecularly to use error correcting, noncovalent assembly to achieve long-range order. This review will focus on the use of supramolecular chemistry to study combinatorial, hierarchical organic systems with emergent optoelectronic properties. Specifically, we will describe systems that undergo excited state deactivation by charge transfer (CT), singlet fission (SF), and Förster resonance energy transfer (FRET). Adopting combinatorial, supramolecular assembly to study emergent photophysics promises to rapidly accelerate progress in this research field.